Glove with medicated porous beads

ABSTRACT

An elastomeric article includes a substrate body formed from an elastomeric material, and a plurality of porous beads capable of containing a treatment within the pores of the beads and dispensing the treatment to an end user.

BACKGROUND OF THE INVENTION

Tightly fitting elastomeric articles, such as surgical and examinationgloves, may be difficult to don due to blocking, the tendency of theglove to stick to itself. As a result, gloves often contain a powderedlubricant on the surface that contacts the skin of the wearer tofacilitate donning. Most commonly, epichlorohydrin treated crosslinkedcornstarch is dusted on the inner surface of the glove duringmanufacturing.

While use of cornstarch does improve the donning characteristics of theglove, it may not be feasible for all applications. One such situationis the use of powders for surgical glove applications. If some of thepowder inadvertently enters the surgical site, it may causecomplications for the patient. For instance, the powder may carry aninfectious agent or the patient may be allergic to the powder.

Other techniques may be used to improve the donning characteristics ofsurgical and examination gloves. These techniques include, for example,manufacturing the glove from a modified latex, using an inner layer of ahydrophilic polymer, applying a slip coating to the inner surface of theglove, and the like. However, as some degree of blocking may still occurwith these techniques, there remains a need for a glove with improveddonning characteristics.

SUMMARY OF THE INVENTION

The present invention generally relates to an elastomeric article, forexample, a glove. The article includes a substrate body formed from anelastomeric material, and a plurality of porous beads covalently bondedto the elastomeric material. The porous beads have pore sizes rangingfrom about 0.01 microns to about 0.5 microns. Within the pores is atreatment that is releasable to the environment. The porous beads maygenerally be formed from a polymer having a vinyl group. The vinyl groupmay be a carbon-carbon vinyl group or an acrylate group. In someembodiments, the environment is the skin of an end-user. The treatmentmay consist of a moisturizer, an ointment, a drug, and an emollient. Insome instances, the article may include from about 0.0001 mass % toabout 10 mass % porous beads. In other instances, the article mayinclude from about 0.001 mass % to about 5 mass % porous beads. In yetother instances, the article may include from about 0.01 mass % to about3 mass % porous beads.

The present invention also relates to an elastomeric article including asubstrate body having a first surface, and a donning layer overlying thefirst surface, where the donning layer includes a polymeric material anda plurality of covalently bonded porous beads. In some instances, thepolymeric material may include a hydrogel. The porous beads have poresizes ranging from about 0.01 microns to about 0.5 microns. Within thepores is a treatment that is releasable to the environment. In someinstances, the donning layer may include from about 0.01 mass % to about80 mass % porous beads. In other instances, the donning layer mayinclude from about 1 mass % to about 50 mass % porous beads. In yetother instances, the donning layer may include from about 10 mass % toabout 25 mass % porous beads.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts an article that may be formed according to the presentinvention, namely a glove.

FIG. 2A depicts a schematic cross-sectional illustration of the articleof FIG. 1 taken along a line 2—2, the article including a substrate bodyand a donning layer, where the donning layer includes a plurality ofcovalently bonded porous beads.

FIG. 2B depicts another schematic cross-sectional illustration of thearticle of FIG. 1 taken along a line 2—2, the article including asubstrate body, a donning layer, and a lubricant layer, where thedonning layer includes a plurality of covalently bonded porous beads.

DESCRIPTION OF THE INVENTION

The present invention generally relates to an elastomeric article havingimproved donning characteristics, for example a condom or glove. As usedherein, the term “elastomeric article” refers to an article formedpredominantly from an elastomeric material. The article includes aplurality of porous beads on the wearer-contacting surface of thearticle to facilitate donning and to contain and dispense a treatment.The beads are covalently bonded to the material that forms the article,so no separate binder material is needed to affix the beads to thearticle. The beads cause the overall surface area of thewearer-contacting surface to be reduced, thereby facilitating donning.The beads are also capable of containing and dispensing, over time, atreatment that may provide a desirable benefit to an end user. To betterunderstand the present invention, a more detailed description isprovided below.

An elastomeric article to be formed, for example, a glove 20 (FIG. 1)includes an inside, or wearer-contacting, surface 22 and an outsidesurface 24. The inside surface 22 has a textured topography due to thepresence of a plurality of porous beads 34 (best seen in FIGS. 2A and2B) covalently bonded to the material that forms the inside surface 22.As used herein, the term “inside surface” refers to the surface of thearticle that contacts the body of the wearer. As used herein, the term“outside surface” refers to the surface of the article that is distalfrom the body of the wearer. The beads do not extend through the entirethickness of the glove, so the barrier properties of the glove are notcompromised.

The glove includes a substrate body 26 having a first surface 28 and asecond surface 30 (FIG. 2A–2B). As used herein, “first surface” refersto the surface of the substrate body proximal to the body of the wearer.As used herein, “second surface” refers to the surface of the substratebody distal to the body of the wearer.

The article of the present invention may include a single layer ormultiple layers as desired. In a single layer glove including only thesubstrate body, the first surface may form the inside surface of theglove. However, in a multi-layer glove having additional layers proximalto the body of the wearer, the additional layer or layers may each forma portion of the inside surface, or the entire inside surface, asdesired. Likewise, in a single layer glove including only the substratebody, the second surface may form the outside surface of the glove.However, in a multi-layer glove having additional layers distal from thebody of the wearer, the additional layer or layers may each form aportion of the outside surface, or the entire outside surface, asdesired.

For example, as depicted in FIG. 2A, the article may include a donninglayer 32 overlying at least a portion of the first surface 28 of thesubstrate body 26. In such an article, the donning layer 32 forms atleast a portion of the inside surface 22 of the glove 20. In some suchembodiments, the donning layer may include a plurality of porous beads34 covalently bonded to the material that forms the donning layer. Asdepicted in FIG. 2B, the article may also include other layers, such asa lubricant layer 36 that overlies at least a portion of the donninglayer 32. In such an article, the lubricant layer 36 forms at least aportion of the inside surface 22 of the glove 20.

The article of the present invention may be formed from any suitableelastomeric material, and by any suitable technique, for exampledipping, spraying, tumbling, drying, and curing. As used herein, theterm “elastomeric material” refers to a polymeric material that iscapable of being easily stretched or expanded, and will substantiallyreturn to its previous shape upon release of the stretching or expandingforce. In one embodiment, the elastomeric material may include naturalrubber, which is generally provided as a natural rubber latex. Inanother embodiment, the elastomeric material may include nitrilebutadiene rubber, and in particular, may include carboxylated nitrilebutadiene rubber. In other embodiments, the elastomeric material mayinclude a styrene-ethylene-butylene-styrene block copolymer,styrene-isoprene-styrene block copolymer, styrene-butadiene-styreneblock copolymer, styrene-isoprene block copolymer, styrene-butadieneblock copolymer, synthetic isoprene, chloroprene rubber, polyvinylchloride, silicone rubber, or a combination thereof.

The article of the present invention, for example, the glove 20, mayinclude a donning layer 32 overlying at least a portion of the firstsurface 28 of the substrate body 26 (FIG. 2A). The donning layer may beformed from any polymeric material that is capable of facilitatingdonning of the glove. Some examples of suitable materials for thedonning layer 28 include, but are not limited to, polybutadienes, forexample, 1,2-syndiotactic polybutadiene, polyurethanes, acrylicpolymers, and the like.

In one embodiment, the polymeric material that forms the donning layermay include a hydrogel. As used herein, the term “hydrogel” refers to apolymeric material that is capable of absorbing more than 20% its weightin water while maintaining a distinct three-dimensional structure. Ahydrogel may be formed from a variety of hydrophilic monomers. Examplesof monomers that may be used to form a hydrogel that may be suitable foruse with the present invention include hydroxy ethyl methacrylate(HEMA), hydroxy ethyl acrylate (HEA), methacrylic acid (MAA), acrylicacid (AA), vinyl pyrrolidone, acrylamide, dimethyl acrylamide, and soforth. While several hydrophilic monomers are set forth herein, itshould be understood that any hydrophilic monomer may be polymerized toform a hydrogel that may be suitable for use with the present invention.

In some instances, it may be desirable to copolymerize a hydrophobicmonomer with a hydrophilic monomer. By doing so, the mechanicalproperties and the performance characteristics of the resulting hydrogelmay be modified for a particular application. Examples of suchhydrophilic monomers include 2-ethyl hexyl acrylate (EHA), methylmethacrylate, styrene, butyl acrylate, hydroxy propyl methacrylate, andacrylated silicone oligomers. While several hydrophobic monomers are setforth herein, it should be understood that any hydrophobic monomer maybe copolymerized with a hydrophilic monomer to form a hydrogel that maybe suitable for use with the present invention.

Furthermore, more than two monomers may be used to form a hydrogel foruse with the present invention. For instance, a hydrogel may includevarious ratios of HEMA, MAA, and EHA. Any ratio may be suitable for agiven application, and in one embodiment, the ratio of HEMA:MAA:EHA maybe about 5:1:1. Where more hydrophobic character is desired in thehydrogel, the concentration of the EHA may be increased. Thus, theproperties of the hydrogel may be modified for a given application.

In another embodiment, the polymeric material that forms the donninglayer may include an unsaturated styrene-isoprene-styrene (SIS) blockcopolymer having tri- or radial-blocks. In one such embodiment, the SISblock copolymer may have a polystyrene end block content of from about10 mass % to about 20 mass % of the total weight of the SIS blockcopolymer. In another such embodiment, the SIS block copolymer may havea polystyrene end block content of from about 15 mass % to about 18 mass% of the total weight of the SIS block copolymer. Moreover, themolecular weight of the polystyrene end blocks may typically be at leastabout 5,000 grams per mole. Some examples of suitable mid-blockunsaturated SIS block copolymers include, but are not limited to,Kraton® D1107 available from Kraton Polymers and Vector® 511 and Vector®4111 available from Dexco Polymers of Houston, Tex.

In yet another embodiment, the polymeric material that forms the donninglayer may include an unsaturated styrene-butylene-styrene (SBS) blockcopolymer. One example of an SBS block copolymer that may be suitablefor use as a donning layer is commercially available from Dexco Polymers(Houston, Tex.) under the trade name VECTOR® 8508. VECTOR® 8508 isbelieved to be a linear, pure triblock copolymer (containing less than1% diblock copolymer) produced using anionic polymerization. Anotherexample of an SBS polymer that may be suitable for use as a donninglayer is also commercially available from Dexco Polymers (Houston, Tex.)under the trade name VECTOR® 8550.

While various polymeric materials that may be used to form the donninglayer are set forth herein, it should be understood that any suitablepolymeric material may be used as desired.

In accordance with the present invention, the substrate body or thedonning layer may include a plurality of porous beads. The beads mayhave any shape, and in some instances, may have a spherical shape. Inother instances, the beads may have an elliptical shape. In yet otherinstances, the beads may have an irregular shape.

The porous beads may be formed from any material that is capable ofbeing covalently bonded to the material that forms the substrate body orthe donning layer, provided that the bead does not plasticize, dissolve,dissociate, or otherwise degrade during formation of the article.

In general, the beads may be formed from any polymer having a vinylgroup. The vinyl group may then be used to covalently bond the bead tothe material that forms the substrate body or the donning layer, asdesired. In some embodiments, the material may include a carbon-carbonvinyl group. In other embodiments, the material may include an acrylategroup.

The beads of the present invention may be formed in a variety of ways.While various techniques are described herein, it should be understoodthat any other suitable technique may be used.

In one embodiment, the beads may be synthesized to contain the neededvinyl functionality. Where this technique is used, the vinylfunctionality will likely be present throughout the porous bead. Suchmaterials may include polymers, copolymers, terpolymers, and so forth,of monomers having a vinyl group, for example, hydroxy ethylmethacrylate (HEMA), hydroxy ethyl acrylate (HEA), methacrylic acid(MAA), acrylic acid (AA), vinyl pyrrolidone, acrylamide, dimethylacrylamide, 2-ethyl hexyl acrylate (EHA), methyl methacrylate, styrene,butyl acrylate, hydroxy propyl methacrylate, and acrylated siliconeoligomers, and so forth. While several such monomers are set forthherein, it should be understood that any polymeric bead having a vinylfunctional group may be used with the present invention.

In another embodiment, the beads may be formed from a material having ahydroxyl functionality. The beads may then be reacted with a materialhaving the needed vinyl group to introduce the vinyl group into thematerial that forms the bead. Examples of materials that includehydroxyl functionality include polyvinyl alcohol, silica, and copolymersof a monomer with vinyl functionality (e.g., vinyl alcohol) and anothermonomer (e.g., styrene, methyl methacrylate (MMA), ethylene, orpropylene).

In yet another embodiment, the beads may be formed from a material thatdoes not have hydroxyl functionality, but that is capable of beingsubject to a surface conversion to produce hydroxyl groups on thesurface of the bead. Examples of such materials include polymethylmethacrylate (PMMA), polyethylene, polypropylene, melamine resin,carboxylated melamine resin, polyvinyltoluene, polystyrene, copolymersof styrene and butadiene, copolymers of styrene and vinyltoluene,copolymers of styrene and divinylbenzene, and copolymers of styrene andmethacrylic acid. Such beads may then be subjected to a surfaceconversion process by which a hydroxyl group is introduced into thestarting material. For example, PMMA may be subjected to atransesterification process to introduce a hydroxyl group. Othermaterials, such as polypropylene and polyethylene, may be, for example,exposed to ozone followed by heating to introduce the needed hydroxylfunctionality. While exemplary oxidative techniques are set forthherein, it should be understood by those skilled in the art that otheroxidative techniques may be employed as desired. The hydroxyl group maythen be subsequently converted to an acrylate group by reacting it withan appropriate chemistry.

Thus, in one instance, the starting material may include a plurality ofPMMA beads, which do not contain the needed vinyl functionality forlater covalent attachment to the substrate body or the donning layer.The PMMA beads may be suspended in aqueous ethylene glycol. Using acidicor basic conditions to catalyze a transesterification reaction, themethyl group of the PMMA are replaced with hydroxyl groups. The hydroxylgroups are then available for reaction with, for example,2-isocyanatoethyl methacrylate. The isocyanate portion of the2-isocyanatoethyl methacrylate reacts with the hydroxyl-modified PMMAbeads to result in a surface acrylated functional bead. In anotherinstance, the hydroxyl groups may be reacted with glycidyl methacrylate.In this instance, the epoxy portion of the glycidyl methacrylate reactswith hydroxyl-modified PMMA beads to also result in a surface acrylatedfunctional bead.

A number of techniques may be suitable to impart the necessary porosityto the beads. For example, one synthesis technique provides that duringthe emulsion polymerization of the monomers used to make a bead, anotherpolymer is added to the solution. This added polymer would be physicallytrapped in the matrix of the bead, but not chemically attached to thebead. Once the beads have been polymerized with the entrapped polymer,it would then be possible to extract the added polymer using a solventwithin which the added polymer is soluble. Upon extraction of thesoluble polymer, one is left with a bead exhibiting a controllable anddesirable degree of porosity.

Another suitable method for creating porous beads is through theaddition of supercritical carbon dioxide. In this case, the monomerswould be dissolved in the supercritical carbon dioxide fluid.Polymerization of the beads would then be allowed to occur. However, atthe end of the synthesis process, the supercritical carbon dioxide wouldbe released to atmospheric pressure. Upon doing so, the supercriticalcarbon dioxide would expand and generate the desired degree of porosityin the synthesized beads.

In some embodiments, the porosity of the beads could be made to rangefrom about 0.01 microns in diameter up to about 0.5 microns. The beadsmay then be impregnated with a desirable treatment or drug capable of,for example, enhancing the skin health of the user. Typical examples ofsuch treatments include, but are not limited to moisturizers, ointments,drugs, and emollients. Some specific examples of these include but arenot limited to aloe, vitamin E, lanolin, polyethylene glycol, glycerin,and mineral oil.

These treatments could be incorporated into the pores prior to the timethe beads are applied to the glove or in a post operation where thepores are filled by dipping, coating, or immersing the glove in atreatment or respective drug solution. If the latter, the application ofthe treatment would then be followed by a rinse, such as a water rinseto remove excess drug from the surface of the glove. It is desirable tohave the treatment be contained substantially within the pores of thebeads alone. It is understood, however, that some quantity of thetreatment may manifest itself upon the surface of the bead, but theintent is to have the treatment wholly contained within the poresthemselves.

The quantity of treatment that may be incorporated into the porous beadsis a function of the total void volume, i.e., the porosity of the beadwith respect to the total bead. That is, if the pores result in a beadcontaining a 40 percent void volume, the remaining 60 percent wouldcomprise a solid bead, and the 40 percent void volume is available forcontaining the respective treatment. In some embodiments, it may bedesirable to provide void volumes ranging from about 0.1 percent toabout 90 percent of the total volume of an exemplary bead. In otherembodiments, it may be desirable to provide void volumes ranging fromabout 20 percent to about 50 percent of the total volume of an exemplarybead.

The rate at which the drug is released from the beads is typically afunction of the diffusion rate of the treatment through the pores.Additionally, the void volume of the bead, the shear forces placed onthe beads as the article is donned or otherwise exposed to play into thediffusion rate to a lesser extent. The rate of release may be defined bygrams of treatment released from the bead per unit surface area of thebead over a unit of time. Therefore the rate of release can be expectedto increase as the void volume of the pores in the bead increases andthe rate of release will also increase dependent upon the shear rate towhich the bead is subjected.

There are two basic mechanisms for the controlled timed release of thetreatment to the user. The first one is by diffusion of the treatmentfrom the pores in the beads onto the user's hands. This is due to theconcentration gradient between the treatment contained within the poresas compared to the target point, for example, in the case of a glove,the user's hands. The treatment would be at 100% concentration in thepores, whereas the target, i.e., the end user's hands, would have a 0%concentration. In other words, the end user would have no treatment onhis hands prior to donning the glove. This concentration gradient of100% to 0%, causes the treatment to diffuse out of the pores and comeinto contact with the hands. The other mechanism causing the release ofthe treatment is due to the friction of the hand rubbing across thesurface of the porous beads. This would result in a “dragging” shearforce on the treatment at the surface of the pores and cause it to flowout onto the user's hands.

For long procedures it would be advantageous to slow down the rate atwhich a treatment is released from the pores. This will cause it to lastlonger and be more effectively utilized by the end user. On the oppositeside, for short procedures, such as medical examinations, it may beadvantageous to have as much of the treatment come out before theprocedure is completed. This could potentially result in fullutilization of the treatment contained within the beads. One way tospeed up the treatment release rate would be to add a surfactant orsurfactants to the treatment formulation to enhance the ability of thetreatment to “wet out” onto the end user's hand. By allowing thetreatment to wet out from moisture generated by the end user, it standsto reason that this will increase the rate at which the treatment flowsout of the pores in the beads.

Overall, the diffusion rate may be caused to range from a nearinstantaneous release of the treatment from the surface of the pores toa timed release occurring over several hours. As stated above, a nearinstantaneous release may be produced by a “dragging” shear force.

Application of the beads to the article is accomplished as explainedabove. The porous beads are covalently bonded to the material that formsthe substrate body. Where a donning layer is included in the article ofthe present invention, it may be desirable to covalently bond the beads34 to the material that forms the donning layer 32 itself (FIG. 2A). Asstated above, the porous beads may be formed in a variety of manners,including direct synthesis of the porous beads and surface conversion ofpolymeric beads (transesterification coupled with reaction with anappropriate chemistry to attach an acrylate group to the surface). Inone instance, the porous bead may be covalently bonded to a hydrogeldonning layer, which may, for example, be formed from HEMA and othermonomers described above. To do so, the porous beads may be suspendedin, for example, an aqueous solution of the monomers used to form thehydrogel donning layer and a free radical initiator. When free radicalpolymerization is initiated, the monomers form polymer chains that growin length and also incorporate the porous beads into the structure viathe acrylate functionality of the beads. Thus, the beads are covalentlybonded to the hydrogel polymeric material used to form the donning layerof the glove. Additionally, as stated, the treatment may be incorporatedinto the beads either before or after the beads are bonded to thearticle.

The beads may be present in any suitable amount that facilitates donningwithout compromising the physical integrity of the donning layer orimpeding its purpose. In some embodiments, the beads may be present inan amount of about 0.01 mass % to about 80 mass % of the resulting(dried) donning layer. In other embodiments, the beads may be present inan amount of about 1 mass % to about 50 mass % of the resulting (dried)donning layer. In yet other embodiments, the beads may be present in anamount of about 10 mass % to about 25 mass % of the resulting (dried)donning layer.

In some instances, the resulting (dried) donning layer may be present inan amount of about 5 mass % of the resulting (solidified) glove. Thus,in one embodiment, the porous beads may be present in an amount of fromabout 0.0001 mass % to about 10 mass % of the resulting (solidified)glove. In another embodiment, the porous beads may be present in anamount of from about 0.001 mass % to about 5 mass % of the resulting(solidified) glove. In yet another embodiment, the porous beads may bepresent in an amount of from about 0.01 mass % to about 3 mass % of theresulting (solidified) glove.

In some embodiments, a lubricant layer 36 (FIG. 2B) may also overlie atleast a portion of the donning layer 32 to aid in donning the article.In one embodiment, the lubricant layer may include a silicone orsilicone-based component. As used herein, the term “silicone” generallyrefers to a broad family of synthetic polymers that have a repeatingsilicon-oxygen backbone, including, but not limited to,polydimethylsiloxane and polysiloxanes having hydrogen-bondingfunctional groups selected from the group consisting of amino, carboxyl,hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiolgroups. In some embodiments, polydimethylsiloxane and/or modifiedpolysiloxanes may be used as the silicone component in accordance withthe present invention. Some suitable modified polysiloxanes that may beused in the present invention include, but are not limited to,phenyl-modified polysiloxanes, vinyl-modified polysiloxanes,methyl-modified polysiloxanes, fluoro-modified polysiloxanes,alkyl-modified polysiloxanes, alkoxy-modified polysiloxanes,amino-modified polysiloxanes, and combinations thereof.

Examples of some suitable phenyl-modified polysiloxanes include, but arenot limited to, dimethyldiphenylpolysiloxane copolymers, dimethyl andmethylphenylpolysiloxane copolymers, polymethylphenylsiloxane, andmethylphenyl and dimethylsiloxane copolymers. Phenyl modifiedpolysiloxanes that have a relatively low phenyl content (less than about50 mole %) may be particularly effective in the present invention. Forexample, the phenyl-modified polysiloxane may be a diphenyl-modifiedsilicone, such as a diphenylsiloxane-modified dimethylpolysiloxane. Insome embodiments, the phenyl-modified polysiloxane contains phenyl unitsin an amount from about 0.5 mole % to about 50 mole %. In otherembodiments, the phenyl-modified polysiloxane contains phenyl units inan amount less than about 25 mole %. In yet other embodiments, thephenyl-modified polysiloxane contains phenyl units in an amount lessthan about 15 mole %. In one particular embodiment, adiphenylsiloxane-modified dimethylpolysiloxane may be used that containsdiphenylsiloxane units in an amount less than about 5 mole %. In stillanother embodiment, a diphenylsiloxane-modified dimethylpolysiloxane maybe used that contains diphenylsiloxane units in an amount less thanabout 2 mole %. The diphenylsiloxane-modified dimethylpolysiloxane maybe synthesized by reacting diphenylsiloxane with dimethylsiloxane.

As indicated above, fluoro-modified polysiloxanes may also be used withthe present invention. For instance, one suitable fluoro-modifiedpolysiloxane that may be used is a trifluoropropyl modifiedpolysiloxane, such as a trifluoropropylsiloxane modifieddimethyl-polysiloxane. A trifluoropropylsiloxane modifieddimethylpolysiloxane may be synthesized by reacting methyl, 3,3,3trifluoropropylsiloxane with dimethylsiloxane. The fluoro-modifiedsilicones may contain from about 5 mole % to about 95 mole % of fluorogroups, such as trifluoropropylsiloxane units. In another embodiment,the fluoro-modified silicones may contain from about 40 mole % to about60 mole % of fluoro groups. In yet another embodiment, atrifluoropropylsiloxane-modified dimethylpolysiloxane may be used thatcontains 50 mole % trifluoropropylsiloxane units.

Other modified polysiloxanes may be utilized with the present invention.For instance, some suitable vinyl-modified polysiloxanes include, butare not limited to, vinyldimethyl terminated polydimethyl-siloxanes,vinylmethyl and dimethylpolysiloxane copolymers, vinyl-dimethylterminated vinylmethyl and dimethylpolysiloxane copolymers,divinylmethyl terminated polydimethylsiloxanes, and vinylphenylmethylterminated polydimethylsiloxanes. Further, some methyl-modifiedpolysiloxanes that may be used include, but are not limited to,dimethyl-hydro terminated polydimethylsiloxanes, methylhydro anddimethyl-polysiloxane copolymers, methylhydro terminated methyloctylsiloxane copolymers and methylhydro and phenylmethyl siloxanecopolymers. In addition, some examples of amino-modified polysiloxanesinclude, but are not limited to, polymethyl (3-aminopropyl)-siloxane andpolymethyl [3-(2-aminoethyl) aminopropyl]-siloxane.

The particular polysiloxanes described above are meant to includehetero- or co-polymers formed from polymerization or copolymer-izationof dimethylsiloxane cyclics and diphenylsiloxane cyclics ortrifluoropropylsiloxane cyclics with appropriate endcapping units. Thus,for example, the terms “diphenyl modified dimethylpolysiloxanes” and“copoloymers of diphenylpolysiloxane and dimethylpolysiloxane” may beused interchangeably. Moreover, other examples of polysiloxanes that maybe used with the present invention are described in U.S. Pat. No.5,742,943 to Chen and U.S. Pat. No. 6,306,514 to Weikel, et al., whichare incorporated herein in their entirety by reference thereto for allpurposes.

In some embodiments, the lubricant layer may include a siliconeemulsion. One such silicone emulsion that may be suitable for use withthe present invention is DC 365, a pre-emulsified silicone (35% TSC)that is commercially available from Dow Corning Corporation (Midland,Mich.). DC 365 is believed to contain 40–70 mass % water, 30–60 mass %methyl-modified polydimethylsiloxane, 1–5 mass % propylene glycol, 1–5mass % polyethylene glycol sorbitan monolaurate, and 1–5 mass %octylphenoxy polyethoxy ethanol. Another silicone emulsion that may besuitable for use with the present invention is SM 2140, commerciallyavailable from GE Silicones (Waterford, N.Y.). SM 2140 is apre-emulsified silicone (50% TSC) that is believed to contain 30–60 mass% water, 30–60 mass % amino-modified polydimethyl-siloxane, 1–5%ethoxylated nonyl phenol, 1–5 mass % trimethyl-4-nonyloxypolyethyleneoxyethanol, and minor percentages of acetalde-hyde, formaldehyde, and 1,4dioxane. Another silicone emulsion that may be suitable for use with thepresent invention is SM 2169 available from GE Silicones (Waterford,N.Y.). SM 2169 is a pre-emulsified silicone that is believed to contain30–60 mass % water, 60–80 mass % polydimethylsiloxane, 1–5 mass %polyoxyethylene lauryl ether, and a small amount of formaldehyde. Yetanother silicone that may be suitable for use with the present inventionis commercially available from GE Silicones (Waterford, N.Y.) under thetrade name AF-60. AF-60 is believed to contain polydimethylsiloxane,acetylaldehyde, and small percentages of emulsifiers. If desired, thesepre-emulsified silicones may be diluted with water or other solventsprior to use.

In another embodiment, the lubricant layer may contain a quaternaryammonium compound, such as that commercially available from GoldschmidtChemical Corporation of Dublin, Ohio under the trade name VERISOFT®BTMS. VERISOFT® BTMS is believed to contain behnyl trimethyl sulfate andcetyl alcohol. Thus for example, in one embodiment, the lubricant layerincludes a quaternary ammonium compound such as VERISOFT® BTMS and asilicone emulsion such as SM 2169.

In another embodiment, the lubricant may include, for example, acationic surfactant (e.g., cetyl pyridinium chloride), an anionicsurfactant (e.g., sodium lauryl sulfate), a nonionic surfactant, anamphoteric surfactant, or a combination thereof.

In some embodiments, one or more cationic surfactants may be used.Examples of cationic surfactants that may be suitable for use with thepresent invention include, for example, behenetrimonium methosulfate,distearyldimonium chloride, dimethyl dioctadecyl ammonium chloride,cetylpyridinium chloride, methylbenzethonium chloride,hexadecylpyridinium chloride, hexadecyltrimethylammonium chloride,benzalkonium chloride, dodecylpyridinium chloride, the correspondingbromides, hydroxyethylheptadecylimidazolium halides, coco aminopropylbetaine, and coconut alkyldimethylammonium betaine. Additional cationicsurfactants that may be used include methyl bis(hydrogenated tallowamidoethyl)-2-hydroxyethly ammonium methyl sulfate, methylbis(tallowamido ethyl)-2-hydroxyethyl ammonium methyl sulfate, methylbis(soya amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, methylbis(canola amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, methylbis(tallowamido ethyl)-2-tallow imidazolinium methyl sulfate, methylbis(hydrogenated tallowamido ethyl)-2-hydrogenated tallow imidazoliniummethyl sulfate, methyl bis(ethyl tallowate)-2-hydroxyethyl ammoniummethyl sulfate, methyl bis(ethyl tallowate)-2-hydroxyethyl ammoniummethyl sulfate, dihydrogenated tallow dimethyl ammonium chloride,didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride,octyl decyl dimethyl ammonium chloride diamidoamine ethoxylates,diamidoamine imidazolines, and quaternary ester salts.

In some embodiments, one or more nonionic surfactants may be used.Nonionic surfactants typically have a hydrophobic base, such as a longchain alkyl group or an alkylated aryl group, and a hydrophilic chaincomprising a certain number (e.g., 1 to about 30) of ethoxy and/orpropoxy moieties. Examples of some classes of nonionic surfactants thatmay be used include, but are not limited to, ethoxylated alkylphenols,ethoxylated and propoxylated fatty alcohols, polyethylene glycol ethersof methyl glucose, polyethylene glycol ethers of sorbitol, ethyleneoxide-propylene oxide block copolymers, ethoxylated esters of fatty(C₈–C₁₈) acids, condensation products of ethylene oxide with long chainamines or amides, condensation products of ethylene oxide with alcohols,and mixtures thereof.

Specific examples of suitable nonionic surfactants include, but are notlimited to, methyl gluceth-10, PEG-20 methyl glucose distearate, PEG-20methyl glucose sesquistearate, C₁₁₋₁₅ pareth-20, ceteth-8, ceteth-12,dodoxynol-12, laureth-15, PEG-20 castor oil, polysorbate 20,steareth-20, polyoxyethylene-10 cetyl ether, polyoxyethylene-10 stearylether, polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether,polyoxyethylene-20 oleyl ether, an ethoxylated nonylphenol, ethoxylatedoctylphenol, ethoxylated dodecylphenol, or ethoxylated fatty (C₆–C₂₂)alcohol, including 3 to 20 ethylene oxide moieties, polyoxyethylene-20isohexadecyl ether, polyoxyethylene-23 glycerol laurate,polyoxy-ethylene-20 glyceryl stearate, PPG-10 methyl glucose ether,PPG-20 methyl glucose ether, polyoxyethylene-20 sorbitan monoesters,polyoxyethylene-80 castor oil, polyoxyethylene-15 tridecyl ether,polyoxy-ethylene-6 tridecyl ether, laureth-2, laureth-3, laureth-4,PEG-3 castor oil, PEG 600 dioleate, PEG 400 dioleate, oxyethanol,2,6,8-trimethyl-4-nonyloxypolyethylene oxyethanol; octylphenoxypolyethoxy ethanol, nonylphenoxy polyethoxy ethanol,2,6,8-trimethyl-4-nonyloxypolyethylenealkyleneoxy-polyethyleneoxyethanol, alkyleneoxy-polyethyleneoxyethanol;alkyleneoxypolyethyleneoxyethanol, and mixtures thereof.

Additional nonionic surfactants that may be used include water solublealcohol ethylene oxide condensates that are the condensation products ofa secondary aliphatic alcohol containing between about 8 to about 18carbon atoms in a straight or branched chain configuration condensedwith between about 5 to about 30 moles of ethylene oxide. Such nonionicsurfactants are commercially available under the trade name Tergitol®from Union Carbide Corp., Danbury, Conn. Specific examples of suchcommercially available nonionic surfactants of the foregoing type areC₁₁–C₁₅ secondary alkanols condensed with either 9 moles of ethyleneoxide (Tergitol® 15-S-9) or 12 moles of ethylene oxide (Tergitol®15-S-12) marketed by Union Carbide Corp., (Danbury, Conn.).

Other suitable nonionic surfactants include the polyethylene oxidecondensates of one mole of alkyl phenol containing from about 8 to 18carbon atoms in a straight- or branched-chain alkyl group with about 5to 30 moles of ethylene oxide. Specific examples of alkyl phenoleth-oxylates include nonyl condensed with about 9.5 moles of ethyleneoxide per mole of nonyl phenol, dinonyl phenol condensed with about 12moles of ethylene oxide per mole of phenol, dinonyl phenol condensedwith about 15 moles of ethylene oxide per mole of phenol anddiisoctylphenol condensed with about 15 moles of ethylene oxide per moleof phenol. Commercially available nonionic surfactants of this typeinclude Igepal® CO-630 (a nonyl phenol ethoxylate) marketed by ISP Corp.(Wayne, N.J.). Suitable non-ionic ethoxylated octyl and nonyl phenolsinclude those having from about 7 to about 13 ethoxy units.

In some embodiments, one or more amphoteric surfactants may be used. Oneclass of amphoteric surfactants that may suitable for use with thepresent invention includes the derivatives of secondary and tertiaryamines having aliphatic radicals that are straight chain or branched,where one of the aliphatic substituents contains from about 8 to 18carbon atoms and at least one of the aliphatic substituents contains ananionic water-solubilizing group, such as a carboxy, sulfonate, orsulfate group. Some examples of amphoteric surfactants include, but arenot limited to, sodium 3-(dodecylamino)propionate, sodium3-(dodecylamino)-propane-1-sulfonate, sodium 2-(dodecylamino)ethylsulfate, sodium 2-(dimethylamino)octadecanoate, disodium3-(N-carboxymethyl-dodecylamino)propane-1-sulfonate, sodium1-carboxy-methyl-2-undecylimidazole, disodium octadecyliminodiacetate,and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.

Additional classes of suitable amphoteric surfactants includephosphobetaines and phosphitaines. For instance, some examples of suchamphoteric surfactants include, but are not limited to, sodium coconutN-methyl taurate, sodium oleyl N-methyl taurate, sodium tall oil acidN-methyl taurate, cocodimethylcarboxymethylbetaine,lauryl-dimethylcarboxymethylbetaine, lauryldimethylcarboxyethylbetaine,cetyldimethylcarboxymethylbetaine, sodium palmitoyl N-methyl taurate,oleyldimethylgammacarboxypropylbetaine,lauryl-bis-(2-hydroxypropyl)-carboxyethylbetaine, di-sodium oleamidePEG-2 sulfosuccinate, laurylamido-bis-(2-hydroxyethyl) propylsultaine,lauryl-bis-(2-hydroxy-ethyl) carboxymethylbetaine,cocoamidodimethylpropylsultaine, stearylamidodimethylpropylsultaine, TEAoleamido PEG-2 sulfosuccinate, disodium oleamide MEA sulfosuccinate,disodium oleamide MIPA sulfosuccinate, disodium ricinoleamide MEAsulfosuccinate, disodium undecylenamide MEA sulfosuccinate, disodiumwheat germamido MEA sulfosuccinate, disodium wheat germamido PEG-2sulfosuccinate, disodium isostearamideo MEA sulfosuccinate, cocoamidopropyl monosodium phosphitaine, lauric myristic amido propyl monosodiumphosphitaine, cocoamido disodium 3-hydroxypropyl phosphobetaine, lauricmyristic amido disodium 3-hydroxypropyl phosphobetaine, lauric myristicamido glyceryl phosphobetaine, lauric myristic amido carboxy disodium3-hydroxypropyl phosphobetaine, cocoamphoglycinate,cocoampho-carboxyglycinate, capryloamphocarboxyglycinate,lauroamphocarboxy-glycinate, lauroamphoglycinate,capryloamphocarboxypropionate, lauro-amphocarboxypropionate,cocoamphopropionate, cocoamphocarboxy-propionate, dihydroxyethyl tallowglycinate, and mixtures thereof.

In certain instances, one or more anionic surfactants may be used.Suitable anionic surfactants include, but are not limited to, alkylsulfates, alkyl ether sulfates, alkyl ether sulfonates, sulfate estersof an alkylphenoxy polyoxyethylene ethanol, alpha-olefin sulfonates,beta-alkoxy alkane sulfonates, alkylauryl sulfonates, alkylmonoglyceride sulfates, alkyl monoglyceride sulfonates, alkylcarbonates, alkyl ether carboxylates, fatty acids, sulfosuccinates,sarcosinates, octoxynol or nonoxynol phosphates, taurates, fattytaurides, fatty acid amide polyoxyethylene sulfates, isethionates, ormixtures thereof.

Particular examples of some suitable anionic surfactants include, butare not limited to, C₈–C₁₈ alkyl sulfates, C₈–C₁₈ fatty acid salts,C₈–C₁₈ alkyl ether sulfates having one or two moles of ethoxylation,C₈–C₁₈ alkamine oxides, C₈–C₁₈ alkoyl sarcosinates, C₈–C₁₈sulfoacetates, C₈–C₁₈ sulfosuccinates, C₈–C₁₈ alkyl diphenyl oxidedisulfonates, C₈–C₁₈ alkyl carbonates, C₈–C₁₈ alpha-olefin sulfonates,methyl ester sulfonates, and blends thereof. The C₈–C₁₈ alkyl group maybe straight chain (e.g., lauryl) or branched (e.g., 2-ethylhexyl). Thecation of the anionic surfactant may be an alkali metal (e.g., sodium orpotassium), ammonium, C₁–C₄ alkylammonium (e.g., mono-, di-, tri), orC₁–C₃ alkanolammonium (e.g., mono-, di-, tri).

Specific examples of such anionic surfactants include, but are notlimited to, lauryl sulfates, octyl sulfates, 2-ethylhexyl sulfates,lauramine oxide, decyl sulfates, tridecyl sulfates, cocoates, lauroylsarcosinates, lauryl sulfosuccinates, linear C₁₀ diphenyl oxidedisulfonates, lauryl sulfosuccinates, lauryl ether sulfates (1 and 2moles ethylene oxide), myristyl sulfates, oleates, stearates, tallates,ricinoleates, cetyl sulfates, and so forth.

The article of the present invention features enhanced donningcharacteristics. The presence of covalently bonded porous beads withinthe article decreases the overall coefficient of friction of thesurface, permits the glove to be donned more readily, and enables theapplication of a desirable treatment to be imparted to the end userwearing or otherwise contacting the article. Further, since theparticles are chemically covalently bonded the article, no additionalbinder is needed. This provides a processing advantage over otherparticulate compositions that require use of a binder to ensure thatparticles will not inadvertently dissociate from the glove.Additionally, where a lubricant is utilized in accordance with thepresent invention, donning is further enhanced.

The invention may be embodied in other specific forms without departingfrom the scope and spirit of the inventive characteristics thereof. Thepresent embodiments therefore are to be considered in all respects asillustrative and not restrictive, the scope of the invention beingindicated by the appended claims rather than by the foregoingdescription, and all changes which come within the meaning and range ofequivalency of the claims are therefore intended to be embraced therein.

1. An elastomeric article comprising: a substrate body including a hydrocarbon-based elastomeric polymeric matrix; a plurality of porous beads having a pore size that ranges from about 0.01 microns to about 0.5 microns, the beads containing a treatment impregnated within said pores, the treatment being time-releasable to an environment; and each of said beads has a surface with at least a vinyl functional group, and said bead is covalently bonded to said elastomeric polymer matrix or a coating thereon.
 2. The article according to claim 1, wherein said vinyl group is selected from the group consisting of a carbon-carbon vinyl group and an acrylate group.
 3. The article according to claim 1, wherein said porous bead has a porosity of about 0.1% to about 90% of the entire volume of said bead.
 4. The article according to claim 3, wherein said porous bead has a porosity of about 20% to about 90% of the entire volume of said bead.
 5. The article according to claim 1, wherein said porous beads are present in an amount of from about 0.0001 mass % to about 10 mass % of said article.
 6. The article according to claim 1, wherein said porous beads do not plasticize, dissolve, dissociate, or degrade during formation of said article.
 7. The ankle according to claim 1, wherein said porous beads arc formed from a material that either has or does not have hydrocyl functionality, but can be surface converted to produce hydroxyl groups on a surface of said beads.
 8. The article according to claim 1, wherein either a diffusion mechanism or a shearing force mechanism is employed to control timed-release of said treatment.
 9. The article according to claim 1, wherein said treatment includes a moisturizer, an ointment, a drug, or an emollient.
 10. The article according to claim 1, wherein said treatment enhances skin-health.
 11. The article according to claim 10, wherein said treatement is selected from the group consisting of aloe, vitamin E, lanolin, polyethylene glycol, glycerin, and mineral oil.
 12. The article according to claim 1, wherein said environment comprises an end user's skin.
 13. The article according to claim 1, wherein said coating on said elastomer polymer matrix comprises a donning layer.
 14. The article according to claim 1, wherein said porous beads are present in an amount of about 0.01 mass % to about 80 mass % of said donning layer.
 15. The article according to claim 1, wherein said porous beads are present on an inside surface.
 16. An elastomeric article comprising: an elastomeric substrate body having a first surface; and a donning layer overlying said first surface, the donning layer comprising a polymer material containing a plurality of porous beads with a surface having reactive vinyl functional groups, said beads are covalently bonded to either said substrate body or said donning layer by means of a C—C bond.
 17. The elastomeric article according to claim 16, where said beads contain a time-releasable treatment in a number of pores.
 18. The elastomeric article according to claim 16, wherein said polymer material comprises a hydrogel.
 19. The elastomeric article according to claim 16, wherein said elastomeric substrate body has a second surface distal from said donning layer, and said second surface contains a plurality of porous beads covalently attached to said second surface.
 20. The article according to claim 16, wherein said article is either a glove or a condom. 